JP2996990B2 - Improved production method of hydrocarbon-aromatic hydroxyl-containing resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a hydrocarbon-aromatic hydroxyl containing resin,
Especially phenolic or substituted phenolic hydrocarbon resins,
And more particularly to phenoldicyclopentadiene resins.

Vegter et al. In U.S. Pat.No. 3,536,734, Nelson
U.S. Pat.No. 4,390,680 and Nelson et al. In U.S. Pat.No. 4,394,497 react unsaturated unsaturated hydrocarbons such as cyclopentadiene or oligomers thereof and phenol or substituted phenol with phenol in the presence of Lewis acid catalysts. And then removing the excess phenol to produce a resin. Phenol - When using a BF ₃ as a catalyst for the preparation of hydrocarbon resins, phenol comprises a detrimental corrosive fluorine-containing compounds in pipes and containers phenol recovery system when removed from the product. Accordingly, it is desirable to have an effective way to reduce or eliminate the amount of corrosive elements in the phenol recovered from the reaction mixture in the production of such phenol-hydrocarbon resins.

The present invention relates to the use of unsaturated hydrocarbons or mixtures of unsaturated hydrocarbons in the presence of a Lewis acid catalyst in the presence of one or two aromatic rings, at least one phenolic hydroxyl group and at least one phenolic hydroxyl group. Reaction with a compound having two ortho or para positions for alkylation (hereinafter referred to as aromatic hydroxyl-containing compound) or a mixture thereof, neutralizing the Lewis acid catalyst by adding an inorganic base, and then reacting the unreacted aromatic hydroxyl A method for producing a hydrocarbon-aromatic hydroxyl-containing resin, comprising removing a compound containing an unreacted aromatic hydroxyl-containing compound without removing a salt formed as a result of neutralization of the Lewis acid catalyst. Removal, thereby obtaining a product which is essentially free of corrosive Lewis acids. That.

The method of reacting the unsaturated hydrocarbon with the aromatic hydroxyl-containing compound is best performed in two stages.

In the first step, the unsaturated hydrocarbon is preferably added at 40 ° C.
130 ° C, more preferably 50 ° C to 100 ° C, most preferably 60 ° C to
At a temperature of 90 ° C., a time sufficient to complete the addition of the unsaturated hydrocarbon while maintaining the exothermic reaction temperature within the above range,
Preferably, the mixture is slowly run over a mixture of the aromatic hydroxyl-containing compound and a suitable catalyst over a period of from 0.25 to 8 hours, more preferably from 0.5 to 6 hours, most preferably from 1 to 4 hours.

If a temperature below 40 ° C. is used in the first step, the desired reaction will not proceed at a suitable rate. In the first step
When a temperature of 130 ° C. or higher is used, particularly when dicyclopentadiene is used, the decomposition of the unsaturated hydrocarbon occurs.

In the first step, any pressure above or below atmospheric pressure is suitable. However, preferably 89.57-413.4 kP
a, more preferably 96.46-275.6 kPa, most preferably 96.46
A pressure of 20206.7 kPa is used. 89.5 in the first step
If a pressure of 7 kPa or less is used, the reactants or catalyst will volatilize. When a pressure of 413.4 kPa or more is used in the first step, a special high-pressure reactor and processing equipment are required.

In the second step, the reaction mixture of the first step is preferably
At a temperature of from 90C to 180C, more preferably from 140C to 150C, for a time sufficient to substantially complete the reaction between the unsaturated hydrocarbon and the aromatic hydroxyl containing compound, preferably from 1 to 8C. Hours, more preferably 2 to 6 hours, most preferably 3 hours
Cook for ~ 4 hours.

If a temperature below 90 ° C. is used in the second step, the reaction intermediate does not transition to form the desired product. When a temperature of 130 ° C. or higher is used in the second step, particularly when dicyclopentadiene is used, the decomposition of the unsaturated hydrocarbon occurs.

In the second step, any pressure above or below atmospheric pressure is suitable. However, preferably 89.57-413.4 kPa,
More preferably 96.46-275.6 kPa, most preferably 96.46-20
A pressure of 6.7 kPa is used. 89.57 kPa in the second step
When the following pressures are used, volatilization of the reactants or catalyst occurs. When a pressure of 413.4 kPa or more is used in the second step, a special high-pressure reactor and processing equipment are required.

Higher reaction temperatures require shorter reaction times, while lower reaction temperatures require longer reaction times.

Preferably, the unsaturated hydrocarbon and aromatic hydroxyl containing compound is a 1: 1 to 20: 1, more preferably 2: 1 to 15: 1, most preferably 3: 1 to 10: 1 unsaturated hydrocarbon. The reaction is performed in an amount that gives the molar ratio of the aromatic hydroxyl-containing compound to hydrogen. If the molar ratio of aromatic hydroxyl-containing compound to unsaturated hydrocarbon is greater than 20: 1, the excess reactants will reduce the capacity of the reactor and thus the effective yield. No advantage is seen in performing the reaction at a high molar ratio of 20: 1 or more. If the molar ratio of aromatic hydroxyl-containing compound to unsaturated hydrocarbon is less than 1: 1, incomplete reaction of the unsaturated hydrocarbon will occur, thus preventing complete conversion of the reactants to the desired product.

If desired, the resinous product may be recovered from the reaction mixture, for example, by removing excess aromatic hydroxyl-containing compounds from the reaction mixture by distillation or other known purification methods. In some cases, resinous products containing excess aromatic hydroxyl-containing compounds may be used without any purification of the reactants. In the production of epoxy resins, for example, the epihalohydrin is mixed with the reactants by the particular method used for this production and reacted in the presence of a suitable catalyst, and the resulting halohydrin intermediate product is converted to a basic compound, such as an alkali metal or alkaline earth. It may be converted to glycidyl ether by reaction with a class of metal hydroxide, carbonate or bicarbonate. As another explanation, in the manufacture of cyanate resins, the reactants may be purified or directly reacted with cyanogen chloride or cyanogen bromide to form polycyanate resins without purification.

Suitable unsaturated hydrocarbons that may be used are, for example, Vegter et al., U.S. Pat.No. 3,536,734; Nelson U.S. Pat.
No. 0, Gebhart et al., U.S. Pat.No. 3,557,239 and Nelson
US Patent No. 4,167,542.

Particularly suitable unsaturated hydrocarbons which may be used, in either crude or purified state, are, for example, butadiene, isoprene, piperylene, cyclopentadiene, cyclopentene, 2-methylbutene-2, cyclohexene, cyclohexadiene, methylcyclopentadiene, Cyclopentadiene, limonene, dipentene, linear or cyclic dimer of piperylene, methyldicyclopentadiene,
Including dimethyldicyclopentadiene, norbornene, norbornadiene, ethylidene norbornene and mixtures thereof. Suitable unsaturated hydrocarbons that may also be used are
For example, other dimers, codimers, oligomers, and co-oligomers of the unsaturated hydrocarbons. Particularly suitable unsaturated hydrocarbons which may be used are, for example, 70 to 100% by weight of dicyclopentadiene; cyclopentadiene - isoprene, cyclopentadiene - piperylene, cyclopentadiene - a C ₄ -C ₆ dienes as methylcyclopentadiene C ₉ -C ₁₂ dimers or co dimers, and / or isoprene, piperylene and 0-30 weight percent dimer of methylcyclopentadiene; C ₄ -C ₉ dienes C ₁₄
Dicyclopentadiene containing from 0 to 7 weight percent of a _C18 trimer and from 0 to 10 weight percent of an aliphatic diolefin such as piperylene, isoprene, 1.5-hexadiene and a cyclic olefin such as cyclopentadiene, methylcyclopentadiene and cyclopentene. Contains concentrates. The process for producing this dicyclopentadiene concentrate is:
See US Pat. No. 3,557,239 to Gebhart et al. And US Pat. No. 4,167,542 to Nelson.

Also, particularly suitable unsaturated hydrocarbons which may be used are 10 to 70 weight percent dicyclopentadiene, C ₄ -C ₆ co dimers and dimeric 1 to 10% of the hydrocarbon, C ₄ ~
C 0 percent ₆ diene oligomers and C ₄ -C ₆
Includes a crude dicyclopentadiene stream containing up to 100 percent remaining alkanes, alkenes and dienes.

Particularly suitable unsaturated hydrocarbons that may be used are piperylene or isoprene at 30-70 weight percent, C ₄
~C ₆ C ₉ ~C ₁₂ dimer and codimer diene, and C ₄
~C containing ₆ alkanes, the remainder comprising crude piperylene or isoprene stream alkenes and dienes to 100% by weight.

Particularly suitable unsaturated hydrocarbons which may be used are, for example, 95 to 100% by weight of dicyclopentadiene and C ₄ -C
₇ Compositions comprising up to 100 weight percent of a saturated or unsaturated hydrocarbon or oligomer thereof.

Particularly suitable unsaturated hydrocarbons which may be used are also the reactants of the hydrocarbon stream described above, for example each of dicyclopentadiene concentrate, crude dicyclopentadiene, crude piperylene or isoprene or in combination with one another or with a high-purity diene stream. Is a hydrocarbon oligomer produced by polymerization.

A suitable aromatic hydroxyl containing compound that may be used is Ve
gter et al., Gebhart et al., and those described in the aforementioned Nelson patent. Such aromatic hydroxyl-containing compounds more preferred for use include, for example, one or two aromatic rings, at least one phenolic hydroxyl group and at least one ortho or para to hydroxyl group effective for alkylation. Includes compounds containing a position. This and other aromatic hydroxyl containing compounds that may be used are described in Vegter et al., Gebhart et al., And Nelson, supra.

Particularly suitable aromatic hydroxyl-containing compounds which may be used are, for example, phenol, chlorophenol, bromophenol, dimethylphenol, o-cresol, m-cresol, p-cresol, hydroquinone, catechol, resorcinol, guaiacol, pyrogallol, phloroglucinol Isopropylphenol, ethylphenol, propylphenol, t-butyl-phenol, isobutylphenol, octylphenol, nonylphenol, cumylphenol, p-phenylphenol, o-phenylphenol, m-phenylphenol, bisphenol A, dihydroxydiphenylsulfone and the like. Of mixtures.

Suitable Lewis acid catalysts that may be used include, for example, Vegter et al., U.S. Pat.No. 3,536,734 and Nelson U.S. Pat.
Includes those described in No. 0,680. In particular it may be used suitable catalysts include, for example _{BF 3, AlCl 3, FeCl 3} , SnCl 4, their coordination complexes and combinations thereof.

The Lewis acid catalyst used in the present invention is used in a catalytically effective amount, that is, an amount that catalyzes the reaction between the unsaturated hydrocarbon and the aromatic hydroxyl-containing compound under the specified reaction conditions. Usually, the amount of catalyst used is preferably between 0.002: 1 and 0.1: 1, more preferably between 0.003: 1 and 0.05: 1,
Most preferably, it comprises an amount that provides a molar ratio of catalyst to aromatic hydroxyl-containing compound of from 0.003: 1 to 0.01: 1.

Suitable inorganic bases that may be used include, for example, alkali metal and alkaline earth metal hydroxides, carbonates and bicarbonates. Particularly suitable such bases that may be used include, for example, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, and combinations thereof. If desired, alkali metal and alkaline earth metal hydroxides may be used as aqueous solutions.

The inorganic base used in the present invention is preferably 1: 1
~ 3: 1, more preferably 1: 1 to 2: 1, most preferably 1: 1 to 1.1:
It is used in an amount to give a molar ratio of base to catalyst of one. When the ratio of base to catalyst is 1: 1 or less, complete neutralization of the catalyst does not occur, and undesirable corrosive catalytic decomposition products remain in the reaction mixture. When the molar ratio of base to catalyst is 3: 1 or more, the molecular weight and viscosity of the product increase significantly.

The neutralization reaction is preferably performed at 30 ° C to 180 ° C, more preferably at 40 ° C.
C. to 160.degree. C., most preferably 40.degree. C. to 150.degree. C. and preferably 89.57 to 413.4 kPa, more preferably a pressure of 96.46 to 206.7 kPa, for a time sufficient to complete the reaction, preferably
The reaction is performed for 0.25 to 4 hours, more preferably 0.5 to 3 hours, and most preferably 1 to 2 hours.

When the neutralization reaction is carried out at a temperature of 30 ° C. or less, the product mixture becomes viscous and cannot be stirred for effective neutralization. When the neutralization reaction is performed at a temperature of 180 ° C. or higher, an undesirable reaction may occur.

When the neutralization reaction is performed at a pressure of about 89.57 kPa or less, the reactants or the catalyst evaporate. About 413.4 kPa for neutralization reaction
When the above pressure is used, a special device is required.

Higher reaction temperatures require shorter reaction times, while lower reaction temperatures require longer reaction times.

 The following examples are illustrative of the present invention.

Example 1 A. Preparation of Dicyclopentadiene-Phenol Resin After mechanical stirring, phenol (2714 g, 28.50 g) was placed in a 5 round bottom flask equipped with a temperature controller and a heating mantle.
84 mol) was melted. While stirring at 70 ° C., BF ₃ etherate (12.38 g, 0.0873 mol) was added. The heating mantle was removed and dicyclopentadiene (381.3 g, 2.88 mol) was added. The reaction temperature was maintained at 70-85 ° C and the addition rate was adjusted to complete in about 1 hour. After the addition of dicyclopentadiene, the reaction temperature was raised to 145 ° C and maintained for 3 hours. The reaction mixture was then cooled to ambient temperature.

Neutralization with B.KOH (molar ratio of KOH with respect to BF ₃ 3.1: 1) 506g reaction mixture from Part A to 1 round-bottomed flask
(Theoretically BF ₃ comprising 0.0147 eq) was added. After heating to about 40 ° C, 6.2 g (0.0485 equivalent) of 44.1% KOH aqueous solution
And the mixture was heated to 145 ° C. At 145 ° C, vacuum was applied and a normal vacuum strip was performed, finishing at 226 ° C and 2 mmHg.

Neutralization with C.KOH (BF ₃ in KOH to the molar ratio 1.1: 1) 447 g of the reaction mixture from Part A to 1 round-bottomed flask
(Theoretically BF ₃ comprising 0.0132 eq) was added. After heating to about 40 ° C, 1.84 g (0.0145 equivalent) of 44.1% KOH aqueous solution
In addition, the mixture was heated to 145 ° C. At 145 ° C,
Apply vacuum and perform normal vacuum strip at 221 ° C and 2mm
Finished with Hg.

Comparative Experiment A To the round bottom flask of 1, 605 g of the reaction mixture of Example 1A was added. After heating to 149 ° C, vacuum was applied to collect excess phenol in three fractions. The vacuum strip was run for one hour and finished at a maximum temperature of 229 ° C. and 2 mmHg.

The excess phenol removed by each vacuum strip from Examples 1B and 1C and Comparative Experiment A was collected in three fractions. The finished product from each fraction and each experiment is
It was analyzed for boron, fluorine and potassium content by line emission spectroscopy.

The average functionality and phenol equivalent of each novolak product was calculated from gel permeation chromatography.

Viscosity measurements are made with a Model 84 program temperature controller and #
Performed on a Brookfield Digital Viscometer Model LVTD equipped with an 18 spindle.

It had no effect on the hydrocarbon novolac be added KOH to neutralize the product characterization BF ₃ catalyst.

Table I shows gel permeation chromatography (GPC) data and viscosities for the control and KOH-modified hydrocarbon novolak products. At KOH: BF ₃ of 3.1: 1, the viscosity of the hydrocarbon novolak increased significantly, but was not affected at 1.1: 1. The GPC data in Table I shows no significant changes in functionality and equivalents, such as the effect of KOH neutralization.

Fluorine and boron distribution The distribution of fluorine and boron in each experiment was determined by analyzing the phenol fraction and each novolak product incorporated during the vacuum stripping process. The results are summarized in Tables II and III. Table II shows the amount (g) of each phenol fraction and each product recovered and the amount (ppm) of fluorine and boron detected in each product and each phenol fraction. Table III shows the fluorine and boron mass balance (g). In each case, the amount of fluorine detected is significantly lower than theory. This is due in part to the formation of HF leaving the system via a cooler that is open to the atmosphere. The discrepancy between the detected amount of boron and the theoretical amount reflects the inaccuracy of the analytical method. However, this data clearly shows in control experiments that significant amounts of fluorine and boron were taken up by phenol during the vacuum strip. On the other hand, the addition of KOH to the novolak before vacuum stripping the phenol provides the desired purpose of preventing sufficient incorporation of boron and fluorine during stripping.

Example 2 Preparation of Phenol-Dicyclopentadiene Novolac in a 10 Gallon Pilot Plant Reactor Using a KOH Neutralization Step Melting phenol (25 kg, 265.7 mol) in a stainless steel 10 gallon reactor and stirring at 56 ° C. BF ₃
Etherate (113.55 g, 0.8 mol) was added. About 65-77
Dicyclopentadiene (3484 g, 26.4 mol) was flowed over 128 minutes while maintaining a temperature of ° C. and a pressure of about 130.9 kPa to 165.4 kPa. After the completion of the dicyclopentadiene addition, the temperature was raised to 145 ° C., and the pressure was maintained at 165.4 to 220.5 kPa and maintained for 3 hours. The reaction mixture was then cooled to 60 ° C and aqueous KOH (44.
111.57 g (0.89 mol) of a 1% aqueous KOH solution) was added.
The mixture was heated to 145 ° C. and a vacuum strip was started to remove excess phenol. Vacuum stripping was continued for 340 minutes while maintaining a temperature of 151 ° C to 180 ° C and a pressure of 4.13 to 55.1 kPa. After this, 177 ° C to 180 ° C and 4.13 to 8.
A steam strip was performed at 27 kPa for 30 minutes. The steam was then turned off and vacuum stripping continued at 177 ° C. to 180 ° C. and about 8.27 kPa for an additional 32 minutes. Almost 6.89kg
Was recovered.

The product had a Mettler softening point of 92.2 ° C and a viscosity of 465 centipoise (measured at 130 ° C with a Brookfield viscometer). The average functionality measured by gel permeation chromatography was 2.32 and the phenol equivalent was 165.7. This product contains 7940 ppm total fluorine and
The phenol recovered from the vacuum and steam stripping steps contained 800 ppm total boron while <100 ppm (detection limit) total fluorine and 20-27 ppm total boron.

Claims (6)

(57) [Claims] In the presence of a Lewis acid catalyst, the unsaturated hydrocarbon or mixture of unsaturated hydrocarbons is reacted with one or two aromatic rings, at least one phenolic hydroxyl group and at least one hydroxyl group. Reacting with a compound having one ortho or para position for alkylation (hereinafter referred to as an aromatic hydroxyl-containing compound) or a mixture thereof; adding an inorganic base to neutralize the Lewis acid catalyst; A method for producing a hydrocarbon-aromatic hydroxyl-containing resin, comprising removing a hydroxyl-containing compound, comprising removing unreacted aromatic hydroxyl-containing compound without removing salts formed as a result of neutralization of the Lewis acid catalyst. A method characterized in that: 2. The method of claim 1, wherein (a) the aromatic hydroxyl-containing compound and the unsaturated hydrocarbon are used in an amount to give a molar ratio of the aromatic hydroxyl-containing compound to the unsaturated hydrocarbon of 1: 1 to 20: 1. Using a Lewis acid catalyst in an amount that provides a molar ratio of Lewis acid to aromatic hydroxyl-containing compound of from 1: 1 to 0.1: 1, and (c) an amount that provides a molar ratio of inorganic base to Lewis acid of 1: 1 to 3: 1. (D) conducting the reaction between the unsaturated hydrocarbon and the aromatic hydroxyl-containing compound at a temperature between 40 ° C. and 180 ° C., and (e) reacting the unsaturated hydrocarbon with the aromatic hydroxyl-containing compound. The method according to claim 1, wherein the reaction is carried out for 1.25 to 16 hours, (f) the neutralization reaction is carried out at a temperature of 30 to 180 ° C, and (g) the neutralization reaction is carried out for 0.25 to 4 hours. 3. Use of an aromatic hydroxyl-containing compound and an unsaturated hydrocarbon in an amount that provides (a) a molar ratio of the aromatic hydroxyl-containing compound to the unsaturated hydrocarbon of 2: 1 to 15: 1, and (b) 0.003 Using a Lewis acid catalyst in an amount that provides a molar ratio of Lewis acid to aromatic hydroxyl-containing compound of 1: 1 to 0.05: 1, and (c) an amount that provides a molar ratio of inorganic base to Lewis acid of 1: 1 to 2: 1. (D) reacting between the unsaturated hydrocarbon and the aromatic hydroxyl-containing compound at a temperature between 50-160 ° C., and (e) reacting between the unsaturated hydrocarbon and the aromatic hydroxyl-containing compound. The method according to claim 1, wherein the reaction is carried out for 2.5 to 12 hours, (f) the neutralization reaction is carried out at a temperature of 30 ° C to 160 ° C, and (g) the neutralization reaction is carried out for 0.5 to 3 hours. 4. Use of (a) an aromatic hydroxyl-containing compound and an unsaturated hydrocarbon in an amount to give a molar ratio of the aromatic hydroxyl-containing compound to the unsaturated hydrocarbon of 3: 1 to 10: 1, and (b) 0.003 Using a Lewis acid catalyst in an amount that provides a molar ratio of Lewis acid to aromatic hydroxyl-containing compound of from 1: 1 to 0.01: 1, and (c) an amount that provides a molar ratio of inorganic base to Lewis acid of 1: 1 to 1.1: 1. (D) conducting the reaction between the unsaturated hydrocarbon and the aromatic hydroxyl-containing compound at a temperature between 60 ° C. and 150 ° C., and (e) reacting the unsaturated hydrocarbon with the aromatic hydroxyl-containing compound. (F) the reaction between the unsaturated hydrocarbon and the aromatic hydroxyl-containing compound for 4 to 8 hours, (g) the neutralization reaction at 40 ° C to 150 ° C. (H) The neutralization reaction is performed at 89.57 to 413.4 kPa. Performed with a force, (i) performing neutralization reaction for 1-2 hours, The method of claim 1, wherein. A wherein (a) said aromatic hydroxyl-containing compound is a phenol, (b) said unsaturated hydrocarbon is dicyclopentadiene, a BF ₃ is (c) said Lewis acid catalyst, and (d The method according to any one of claims 1 to 4, wherein the inorganic base is an alkali metal hydroxide. 6. The method according to claim 5, wherein said inorganic base is potassium hydroxide.